US8748663B2 - Curing activators - Google Patents

Curing activators Download PDF

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Publication number
US8748663B2
US8748663B2 US13/500,874 US201013500874A US8748663B2 US 8748663 B2 US8748663 B2 US 8748663B2 US 201013500874 A US201013500874 A US 201013500874A US 8748663 B2 US8748663 B2 US 8748663B2
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chch
curing
mix
molecular formula
activators
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US20120259140A1 (en
Inventor
Salvatore Cotugno
Paolo Straffi
Barbara Secchi
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Bridgestone Corp
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Bridgestone Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds

Definitions

  • the present invention relates to curing activators.
  • curing a rubber mix calls for special additives, including curing activators and accelerating agents.
  • booster accelerating agents are used.
  • Fatty acids are also commonly used as curing activators, but, though effective in activating the curing process, may result in a reduction in adhesion of the green mix.
  • Fatty acids in fact, by reacting with zinc oxide, may produce, as an undesired by-product, zinc salts which tend to migrate towards the surface of the mix, thus reducing adhesion of the green mix.
  • the present invention relates to use of compounds of molecular formula (I) as curing activators of mixes comprising a cross-linkable unsaturated-chain polymer base; ([R 1 R 2 R 3 NR 5 (NR 4 R 6 R 7 ) n] (n+1)+ ) y ( n+ 1)X y ⁇ (I) where:
  • X is an anionic atom or group
  • R 1 , R 2 and R 3 which may be the same or different, are each C m H 2m+1 , where m ranges between 1 and 3, or CH 2 CHCH 2 or CHCHCH 3
  • R 4 , R 6 and R 7 which may be the same or different, are each CH 2 CHCH 2 or CHCHCH 3
  • n 0 or 1
  • y is 1 when n is 1; y is 1 or 2 when n is 0
  • R 5 is an aliphatic group C 15 -C 22 when n is 0; and is an aliphatic group C 8 -C 16 when n is 1
  • R 1 , R 2 and R 3 are preferably CH 2 CHCH 2 , and, more preferably, n is 1 and R 5 is a saturated aliphatic group.
  • R 5 comprises a double bond, and n is 0.
  • the curing activator preferably has a molecular formula in the group comprising: [(CH 3 ) 3 N(CH 2 ) 8 CHCH(CH 2 ) 7 CH 3 ] + X ⁇ ; [(CH 2 CHCH 2 ) 3 N(CH 2 ) 15 CH 3 ] + X ⁇ ; [(CH 3 )(CH 2 CHCH 2 ) 2 N(CH 2 ) 15 CH 3 ] + X ⁇ ; [(CH 2 CHCH 2 )(CH 3 ) 2 N(CH 2 ) 15 CH 3 ] + X ⁇ ; e [(CH 2 CHCH 2 ) 3 N(CH 2 ) 12 N(CH 2 CHCH 2 ) 3 ] 2 + 2X ⁇ .
  • X ⁇ is I ⁇ or Br ⁇ .
  • 0.01 to 10 phr of the curing activator is used in the mix.
  • the present invention also relates to a mix comprising a cross-linkable unsaturated-chain polymer base, characterized by comprising a compound of molecular formula (I) as a curing activator.
  • the present invention also relates to a rubber product, characterized by being made from a mix comprising a compound of molecular formula (I) as a curing activator.
  • the present invention also relates to a tyre, characterized by comprising at least one rubber part made from a mix comprising a compound of molecular formula (I) as a curing activator.
  • the five curing activators were as follows:
  • Ten mixes (A 1 , A 2 , B 1 , B 2 , C 1 , C 2 , D 1 , D 2 , E 1 , E 2 ) were prepared, each comprising one of the above five curing activators (a, b, c, d, e) according to the present invention. More specifically, the five different curing activators (a, b, c, d, e) were used in two different concentrations.
  • Table I shows the compositions in phr of the above mixes.
  • a control mix (MC TBBS ) was prepared comprising fatty acids as activators, as opposed to the curing activators of the mixes in Table I.
  • Table II shows the composition in phr of the control mix.
  • a control mix (MC DPG ) was prepared comprising no curing activators, and only comprising DPG and fatty acids as activators.
  • Table III shows the compositions in phr of mixes C 3 , C 4 , E 3 , E 4 and the control mix MC DPG .
  • Table IV shows the rheometric property results of the TBBS mixes. The curing tests were performed at temperatures of 145° C., 160° C., 175° C. and 195° C. The MH and ML values are expressed in dNM, and T'10 and T'90 in minutes.
  • Table V shows the rheometric property results of the DPG mixes. The curing tests were performed at a temperature of 160° C.
  • Table V does not show the results of the control mix MC DPG .
  • the curing activators according to the present invention provide for a surprisingly significant increase in the effectiveness of the accelerating agents used with them. This constitutes a major advantage in terms of production, as well as a valid alternative to booster accelerating agents widely used in the rubber industry, and some of which are currently under investigation by health protection agencies.
  • the curing activators according to the present invention also surprisingly provide for limiting use of fatty acids in the mix as activators, which has the advantage of solving the green-rubber adhesion problems posed by salts migrating towards the surface of the mix.
  • Zinc salts in fact, are formed as an undesired byproduct of fatty acids reacting with zinc oxide.
  • the present invention may be used to advantage in industries involving the manufacture of fast-cured rubber products, in particular, and preferably, the tyre industry.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Suspension Of Electric Lines Or Cables (AREA)
  • Vehicle Body Suspensions (AREA)

Abstract

Use of compounds of molecular formula (I) as curing activators of mixes having a cross-linkable unsaturated-chain polymer base: ([R1R2R3NR5(NR4R6R7)n](n+1)+)y(n+1)Xy− (I); where: X is an anionic atom or group; R1, R2 and R3, which may be the same or different, are each CmH2m+1, where m ranges between 1 and 3, or CH2CHCH2 or CHCHCH3; R4, R6 and R7, which may be the same or different, are each CH2CHCH2 or CHCHCH3; n is 0 or 1; y is 1 when n is 1; y is 1 or 2 when n is 0; R5 is an aliphatic group C15-C22 when n is 0; and is an aliphatic group C8-C16 when n is 1; when n is 0, at least one of R1, R2, R3 and R5 comprises a double bond.

Description

CROSS REFERENCE TO RELATED APPLICATIONS
This application is a National Stage of International Application No. PCT/IB2010/002546 filed Oct. 7, 2010, claiming priority based on Italian Patent Application No. TO2009A000765 filed Oct. 7, 2009, the contents of all of which are incorporated herein by reference in their entirety.
TECHNICAL FIELD
The present invention relates to curing activators.
BACKGROUND ART
To achieve specific results, curing a rubber mix calls for special additives, including curing activators and accelerating agents.
In some industrial applications requiring fast curing, highly effective, booster accelerating agents are used.
Some of these have recently come under attack for health reasons.
Fatty acids are also commonly used as curing activators, but, though effective in activating the curing process, may result in a reduction in adhesion of the green mix. Fatty acids, in fact, by reacting with zinc oxide, may produce, as an undesired by-product, zinc salts which tend to migrate towards the surface of the mix, thus reducing adhesion of the green mix.
A need is therefore felt for new curing activator systems designed to ensure fast curing, while at the same time limiting use of fatty acids.
DISCLOSURE OF INVENTION
The present invention relates to use of compounds of molecular formula (I) as curing activators of mixes comprising a cross-linkable unsaturated-chain polymer base;
([R1R2R3NR5(NR4R6R7)n] (n+1)+)y(n+1)Xy−  (I)
where:
X is an anionic atom or group
R1, R2 and R3, which may be the same or different, are each CmH2m+1, where m ranges between 1 and 3, or CH2CHCH2 or CHCHCH3
R4, R6 and R7, which may be the same or different, are each CH2CHCH2 or CHCHCH3
n is 0 or 1
y is 1 when n is 1; y is 1 or 2 when n is 0
R5 is an aliphatic group C15-C22 when n is 0; and is an aliphatic group C8-C16 when n is 1
when n is 0, at least one of R1, R2, R3 and R5 comprises a double bond.
R1, R2 and R3 are preferably CH2CHCH2, and, more preferably, n is 1 and R5 is a saturated aliphatic group.
Preferably, R5 comprises a double bond, and n is 0.
The curing activator preferably has a molecular formula in the group comprising:
[(CH3)3N(CH2)8CHCH(CH2)7CH3]+X−;
[(CH2CHCH2)3N(CH2)15CH3]+X−;
[(CH3)(CH2CHCH2)2N(CH2)15CH3]+X−;
[(CH2CHCH2)(CH3)2N(CH2)15CH3]+X− ; e
[(CH2CHCH2)3N(CH2)12N(CH2CHCH2)3]2 +2X−.
Preferably, X− is I− or Br−.
Preferably, 0.01 to 10 phr of the curing activator is used in the mix.
The present invention also relates to a mix comprising a cross-linkable unsaturated-chain polymer base, characterized by comprising a compound of molecular formula (I) as a curing activator.
The present invention also relates to a rubber product, characterized by being made from a mix comprising a compound of molecular formula (I) as a curing activator.
The present invention also relates to a tyre, characterized by comprising at least one rubber part made from a mix comprising a compound of molecular formula (I) as a curing activator.
BEST MODE FOR CARRYING OUT THE INVENTION
The following are purely non-limiting examples for a clearer understanding of the invention.
Examples
In the examples below, five different compounds (a, b, c, d, e) in the class of curing aids according to the present invention were employed.
The five curing activators were as follows:
    • compound (a) of molecular formula [(CH3)3N(CH2)8CHCH(CH2)7CH3]+I−
    • compound (b) of molecular formula [(CH2CHCH2)3N(CH2)15CH3]+Br—
    • compound (c) of molecular formula [(CH3)(CH2CHCH2)2N(CH2)15CH3]+I−
    • compound (d) of molecular formula [(CH2CHCH2)(CH3)2N(CH2)15CH3]+I−
    • compound (e) of molecular formula [(CH2CHCH2)3N(CH2)12N(CH2CHCH2)3]2 +2Br−
Purely by way of example, the above curing activators were tested using TBBS and DPG accelerating agents as described below.
TBBS Mixes
Ten mixes (A1, A2, B1, B2, C1, C2, D1, D2, E1, E2) were prepared, each comprising one of the above five curing activators (a, b, c, d, e) according to the present invention. More specifically, the five different curing activators (a, b, c, d, e) were used in two different concentrations.
Table I shows the compositions in phr of the above mixes.
TABLE I
A1 A2 B1 B2 C1 C2 D1 D2 E1 E2
S-SER 100
N660 40
ZnO 2
S 2
TBBS 2
comp. (a) 2 5
comp. (b) 2 5
comp. (c) 2 5
comp. (d) 2 5
comp. (e) 2 5
To accurately assess the advantages of mixes comprising the curing activators according to the present invention, a control mix (MCTBBS) was prepared comprising fatty acids as activators, as opposed to the curing activators of the mixes in Table I.
Table II shows the composition in phr of the control mix.
TABLE II
MCTBBS
S-SBR 100
N660 40
FATTY ACIDS 1
ZnO 2
S 2
TBBS 2
DPG Mixes
Four mixes (C3, C4, E3, E4) were prepared comprising curing activators (c) and (e) according to the present invention respectively. As shown below, curing activators (c) and (e) were tested in both the presence and absence of fatty acids.
To accurately assess the advantages of mixes comprising the curing activators according to the present invention, a control mix (MCDPG) was prepared comprising no curing activators, and only comprising DPG and fatty acids as activators.
Table III shows the compositions in phr of mixes C3, C4, E3, E4 and the control mix MCDPG.
TABLE III
C3 C4 E3 E4 MCDPG
S-SBR 100
N660 40
FATTY ACIDS 1 1 1
ZnO 2
S 1
DPG 1
Acc. (c) 1 1
Acc. (e) 1 1
Tests
The mixes with the above compositions were test cured at different temperatures. More specifically, the rheometric properties of each mix were tested as per ISO Standard 6502.
Table IV shows the rheometric property results of the TBBS mixes. The curing tests were performed at temperatures of 145° C., 160° C., 175° C. and 195° C. The MH and ML values are expressed in dNM, and T'10 and T'90 in minutes.
TABLE IV
MCTBBS A1 A2 B1 B2 C1 C2 D1 D2 E1 E2
145° C.
1.81 1.36 1.4 1.76 1.66 1.64 1.48 1.38 1.28 1.29 1.18
22.03 17.79 14.36 17.49 12.05 17.73 15.43 19.58 16.78 18.36 14.7
26.39 5.26 3.3 10.3 5.32 7.53 7.15 4.38 4.22 3.7 3.5
37.64 15.18 25.23 20.53 29.32 17.9 27.52 13.46 23.12 13.36 24.1
160° C.
1.72 1.29 0.61 1.7 1.44 1.02 0.98 1.16 1.06 1.32 1.13
21.23 19.02 13.21 17.38 11.16 18.59 15.04 20.05 16.87 18.2 11.11
8.79 1.68 0.9 2.36 1.7 1.61 1.56 1.96 1.92 2.86 2.59
14.9 7.81 10.56 6.63 10.52 5.41 9.26 6.34 11.58 8.12 10.12
175° C.
1.53 1.12 0.74 1.53 0.98 0.86 0.8 1 0.93 1.2 0.95
21.24 19.65 13.12 17.39 12.62 18.63 15.96 20.32 17.57 18.36 12.44
3.23 0.75 0.49 1.01 0.77 0.77 0.76 0.96 0.94 1.22 1.09
7.09 5.02 5.22 2.68 5.33 2.63 5.18 3.39 4.99 3.92 5.91
195° C.
1.34 0.55 0.74 1.29 1.03 0.79 0.78 0.92 0.84 1.13 0.88
20.77 19.12 14.52 17.42 12.34 18.22 15.46 20.14 17.16 18.18 13
0.94 0.27 0.24 0.46 0.4 0.38 0.39 0.46 0.45 0.51 0.47
2.28 1.27 1.27 1.29 2.9 1.08 2.45 1.42 2.43 1.53 3.38
Table V shows the rheometric property results of the DPG mixes. The curing tests were performed at a temperature of 160° C.
Because curing did not occur at the set conditions, Table V does not show the results of the control mix MCDPG.
TABLE V
C3 C4 E3 E4
ML 1.54 1.05 1.89 1.64
MH 12.31 13.58 15.14 14.2
T10 1.91 2.89 1.83 1.51
T50 4.84 10.17 4.49 4.7
T90 13.92 20.04 12.42 16.61
As the above results clearly show, the curing activators according to the present invention provide for a surprisingly significant increase in the effectiveness of the accelerating agents used with them. This constitutes a major advantage in terms of production, as well as a valid alternative to booster accelerating agents widely used in the rubber industry, and some of which are currently under investigation by health protection agencies.
The curing activators according to the present invention also surprisingly provide for limiting use of fatty acids in the mix as activators, which has the advantage of solving the green-rubber adhesion problems posed by salts migrating towards the surface of the mix. Zinc salts, in fact, are formed as an undesired byproduct of fatty acids reacting with zinc oxide.
As will be clear to anyone skilled in the art, the present invention may be used to advantage in industries involving the manufacture of fast-cured rubber products, in particular, and preferably, the tyre industry.

Claims (7)

The invention claimed is:
1. A method of curing a mix comprising a cross-linkable unsaturated-chain polymer base comprising the step of activating curing by using a compound of molecular formula (I) as a curing activator;

([R1R2R3NR5(NR4R6R7)n] (n+1)+)y(n+1)Xy−  (I)
where:
X is an anionic atom or group
R1, R2 and R3, which may be the same or different, are each CmH2m+1, where m ranges between 1 and 3, or CH2CHCH2 or CHCHCH3
R4, R6 and R7, which may be the same or different, are each CH2CHCH2 or CHCHCH3
n is 0 or 1
y is 1 when n is 1; y is 1 or 2 when n is 0
R5 is an aliphatic group C15-C22 when n is 0; and is an aliphatic group C8-C16 when n is 1 when n is 0, at least one of R1, R2, R3 and R5 comprises a double bond.
2. The method of claim 1, wherein R1, R2 and R3 are CH2CHCH2.
3. The method of claim 2, wherein n is 1 and R5 is a saturated aliphatic group.
4. The method of claim 1, wherein R5 comprises a double bond and n is 0.
5. The method of claim 1, wherein said compounds of molecular formula (I) has a molecular formula selected from the group consisting of:

[(CH3)3N(CH2)8CHCH(CH2)7CH3]+X−;

[(CH2CHCH2)3N(CH2)15CH3]+X−;

[(CH3)(CH2CHCH2)2N(CH2)15CH3]+X−;

[(CH2CHCH2)(CH3)2N(CH2)15CH3]+X− ; e and

[(CH2CHCH2)3N(CH2)12N(CH2CHCH2)3]2 +2X−.
6. The method of claim 1, wherein X− is I− or Br−.
7. The method of claim 1, wherein the mix comprising a cross-linkable unsaturated-chain polymer base comprises sulphur and an accelerating agent.
US13/500,874 2009-10-07 2010-10-07 Curing activators Expired - Fee Related US8748663B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
ITTO2009A000765 2009-10-07
ITTO2009A000765A IT1396300B1 (en) 2009-10-07 2009-10-07 GUIDED AGENTS OF VULCANIZATION.
ITTO2009A0765 2009-10-07
PCT/IB2010/002546 WO2011042799A1 (en) 2009-10-07 2010-10-07 Curing activators

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EP (1) EP2486091B1 (en)
JP (1) JP5721723B2 (en)
CN (1) CN102597086B (en)
ES (1) ES2432998T3 (en)
IT (1) IT1396300B1 (en)
WO (1) WO2011042799A1 (en)

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ITTO20110504A1 (en) * 2011-06-08 2012-12-09 Bridgestone Corp METHOD FOR THE CREATION OF COLORED PORTIONS ON A TIRE
ITTO20110525A1 (en) * 2011-06-15 2012-12-16 Bridgestone Corp METHOD OF VULCANIZATION WITH MICROWAVE OF RUBBER COMPOUNDS
US20150005418A1 (en) * 2011-12-23 2015-01-01 Bridgestone Corporation Coloured tyre portions

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GB1298099A (en) 1969-10-20 1972-11-29 Kendall & Co Unsaturated quaternary ammonium compounds and copolymers containing them
US3780092A (en) 1969-10-20 1973-12-18 Kendall & Co Monomeric emulsion stabilizers
EP0376876A1 (en) 1988-12-28 1990-07-04 The Goodyear Tire & Rubber Company Vulcanizate activator system for rubber compositions
US4960821A (en) 1987-12-21 1990-10-02 Exxon Research And Engineering Company Compatible mixtures of cationic viscoelastic monomer fluids and cationic-alkyl containing copolymers
US5187239A (en) 1988-12-28 1993-02-16 The Goodyear Tire & Rubber Company Sulfur vulcanizable rubber compositions containing a methyl trialkyl ammonium salt
WO2004052983A1 (en) 2002-12-12 2004-06-24 Pirelli Pneumatici S.P.A. Tyre for vehicle wheels and elastomeric composition
WO2010049470A1 (en) 2008-10-30 2010-05-06 Bridgestone Corporation Water-based cement for producing tyres

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JP2000026663A (en) * 1999-07-09 2000-01-25 Goodyear Tire & Rubber Co:The Sulfur vulcanizable rubber composition
JP2001106795A (en) * 1999-10-08 2001-04-17 Daiso Co Ltd N-(polyallyl)ammonium salt-based cross-linking agent
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GB1298099A (en) 1969-10-20 1972-11-29 Kendall & Co Unsaturated quaternary ammonium compounds and copolymers containing them
US3780092A (en) 1969-10-20 1973-12-18 Kendall & Co Monomeric emulsion stabilizers
US4960821A (en) 1987-12-21 1990-10-02 Exxon Research And Engineering Company Compatible mixtures of cationic viscoelastic monomer fluids and cationic-alkyl containing copolymers
EP0376876A1 (en) 1988-12-28 1990-07-04 The Goodyear Tire & Rubber Company Vulcanizate activator system for rubber compositions
US5187239A (en) 1988-12-28 1993-02-16 The Goodyear Tire & Rubber Company Sulfur vulcanizable rubber compositions containing a methyl trialkyl ammonium salt
WO2004052983A1 (en) 2002-12-12 2004-06-24 Pirelli Pneumatici S.P.A. Tyre for vehicle wheels and elastomeric composition
WO2010049470A1 (en) 2008-10-30 2010-05-06 Bridgestone Corporation Water-based cement for producing tyres

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International Search Report of PCT/IB2010/002546, dated Jan. 12, 2011.

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CN102597086B (en) 2014-02-26
WO2011042799A1 (en) 2011-04-14
EP2486091B1 (en) 2013-08-14
ITTO20090765A1 (en) 2011-04-08
IT1396300B1 (en) 2012-11-16
CN102597086A (en) 2012-07-18
JP2013507476A (en) 2013-03-04
EP2486091A1 (en) 2012-08-15
ES2432998T3 (en) 2013-12-05
US20120259140A1 (en) 2012-10-11

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